Base-Metal Catalysis - presented by Prof. Lingling Chu and Assoc. Prof. Ming Joo Koh and Prof. Zhan Lu and Assoc. Prof. Tatsuhiko Yoshino and Prof. Naohiko Yoshikai

Base-Metal Catalysis

Lingling Chu, Ming Joo Koh, Zhan Lu and Tatsuhiko Yoshino

Prof. Lingling ChuAssoc. Prof. Ming Joo KohAssoc. Prof. Tatsuhiko YoshinoProf. Zhan Lu
Slide at 2:16:18
Part II: Ligands regulate the coordination modes and valence states of metals Cobalt (II) hydride species promote olefin insertion migration and asymmetric hydroboration Known literature results: racemic reactions Proposed cobalt (II) hydride species R2 single metal catalyst functional group (FG) FG = Ar, CO2, RCO, CHO, Bpin, SiR3, M = Pd, Rh, Ru, Ir, Zr, Ti, Fe, Co, Ni, Our work: IPPA-Co-H cat. Co(OAc)2 BPin cat. IPPA Flexible coordination mode, d7 cobalt species HBpin M(II)-H bond is weak which could rich up to 99% ee interaction modes Formation of secondary carbon cobalt Cobalt (II) hydride promote olefin insertion migration species Achieved highly enantioselective migration/hydroboration of internal olefins Lu, Z. et al Nat. Commun. 2018, 9, 3939; ACS Catal. 2019, 9, 4025; Angew. Chem. Int. Ed. 2022, 61, e202205619.
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References
  • 1.
    X. Chen et al. (2018) Asymmetric remote C-H borylation of internal alkenes via alkene isomerization. Nature Communications
  • 2.
    X. Chen et al. (2019) Cobalt-Catalyzed Asymmetric Markovnikov Hydroboration of Styrenes. ACS Catalysis
  • 3.
    C. Chen et al. (2022) Cobalt‐Catalyzed Asymmetric Sequential Hydroboration/Isomerization/Hydroboration of 2‐Aryl Vinylcyclopropanes. Angewandte Chemie International Edition
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Summary (AI generated)

Not only could the insertion migration reaction occur, but the cobalt two species could also exhibit 3D metals properties to undergo the hat reaction and produce a radical. In our case, the hydroamination of simple R king could provide the Cairo amine with 86% ee. During the magnum study, we discovered the radical intermediate.